A green deolefination method that completely replaces white clay

Abstract

The present application relates to a kind of green olefin removal method completely replacing clay, which comprises under liquid phase continuous hydrotreating conditions, first, reforming generated oil is mixed with hydrogen through high-efficiency mixer, hydrogen is mixed with reforming generated oil intensively and quickly, and saturated hydrogen-dissolved reforming generated oil is obtained, the saturated hydrogen-dissolved reforming generated oil is sent into first hydrogenation reactor, first contact with nickel-containing catalyst, and the reaction product is then introduced into second hydrogenation reactor, and contact with noble metal-containing catalyst.Reformate is treated by olefin removal, and the product obtained mainly contains benzene, toluene, xylene and other aromatic hydrocarbons, the bromine index of which is less than 20 mgBr / 100g oil, and the loss of aromatic hydrocarbons is less than 0.1wt%.

Description

TECHNICAL FIELD

[0001] The present application relates to a reforming product hydrotreating method, in particular, a high-efficiency liquid-phase hydrogenation reaction treatment unit is arranged between a reforming product separation and stabilizing tower, and is particularly suitable for a continuous reforming device for producing aromatic hydrocarbons. BACKGROUND

[0002] Light aromatic hydrocarbons such as benzene, toluene and xylene (BTX) are important organic chemical raw materials, and are mainly derived from catalytic reforming of naphtha. The reforming product oil is rich in aromatic hydrocarbons and contains a small amount of olefins. Due to the relatively active nature of the olefins (especially trace amounts of dienes), the aromatic extraction in the aromatic hydrocarbon combination device and the performance of the downstream equipment, xylene (PX) adsorbent and catalyst are affected to varying degrees. With the increasing complexity and diversification of the reforming device feedstock (especially the increasing heaviness and poor quality), the severity of the reforming device treatment is increasing, and the olefin content in the reforming product oil is also showing a significant upward trend. Therefore, the pressure on the aromatic refining process is increasing, and most devices still use the traditional industrial granular clay olefin removal process, which will be difficult to adapt to this change, especially for the C8+ mixed aromatic hydrocarbon fraction, which is rich in indane, gum and other heavy components that easily deactivate the clay, resulting in an increasingly high frequency of clay replacement. Some enterprises even need to replace the granular clay every week or so, which not only causes a very high labor intensity, but also requires a large amount of clay. The discarded clay contains a certain amount of heavy aromatic hydrocarbons, and landfill or incineration treatment can cause serious environmental pollution, and the post-treatment cost is also relatively high, resulting in high overall use cost of the clay. In recent years, there have also been methods for non-hydrogenation catalytic olefin removal using molecular sieve-containing olefin removal catalysts, although the service life is longer than that of granular clay, but the single-pass service life is still relatively short, and continuous unloading and regeneration and post-treatment landfill and other environmental protection issues still exist. In addition, since the reaction mechanisms of granular clay and molecular sieve-containing refining catalysts are basically similar, mainly removing olefins through alkylation, polymerization and condensation reactions, etc., resulting in an increase in the content of heavy aromatic hydrocarbons with little value in the reaction product, and an increase in the dry point of the reaction product. Therefore, there is an urgent need for a green and environmentally friendly olefin removal method to completely replace the industrial granular clay and molecular sieve-containing refining catalyst olefin removal methods.

[0003] Selective hydrogenation refers to selective hydrogenation of reforming product oil and raffinate to remove olefins under hydrogenation conditions, without saturating the aromatic hydrocarbons, to achieve deep hydrogenation removal of olefins therein. The catalyst used mainly contains non-noble metal (such as Co-Mo or Ni-Mo) and noble metal (containing Pt, Pd, etc.) catalysts. Conventional sulfided non-noble metal Co-Mo or Ni-Mo hydrogenation refining catalysts are used at relatively high reaction temperatures (300-350°C) and relatively low space velocities (2.0-3.0 h -1) to achieve deep olefin removal (bromine index less than 100 mg Br / 100g oil) and ensure that the loss of aromatics during hydrogenation is less than 0.5wt%. In addition, since the reforming product oil and the reforming hydrogen product do not contain sulfur, the sulfided non-noble metal Co-Mo or Ni-Mo hydrofining catalyst is easily desulfurized, resulting in deactivation. And the sulfur precipitated during regeneration of the Co-Mo or Ni-Mo hydrofining catalyst can seriously contaminate the platinum catalyst in the reforming reactor. The catalyst containing noble metals (containing Pt, Pd, etc.) can deeply remove olefins in the reforming product oil (bromine index of the product is less than 50 mg Br / 100g oil) at a lower reaction temperature (100-250℃) and a higher space velocity (5.0-15.0h -1 ) and ensure that the loss of aromatics during hydrogenation is less than 0.5wt%. Typical foreign ones are the ORP olefin reduction process of UOP Company in the United States and the Arofining process of Axens Company in France, and the common feature of the two processes is that the olefins in the reforming product oil are selectively hydrogenated to saturated hydrocarbons under liquid phase reaction conditions.

[0004] Chinese Patent Application CN103666544A introduces a reforming product oil hydroprocessing method, which uses a catalyst having catalytic hydrogenation effect to contact the reforming product oil in a hydrogenation reactor under liquid phase hydroprocessing conditions, and the hydrogen used in the hydroprocessing is at least partially from the dissolved hydrogen in the reforming product oil. The disadvantage of this process is that only the hydrogen dissolved in the reforming product oil obtained from the reforming product separation tank is used for hydroprocessing, and the quality of the obtained product cannot meet the standard. Nanoscale through holes need to be installed to supplement hydrogen, which requires high equipment.

[0005] Chinese Patent Application CN102911721A discloses a reforming product oil liquid phase selective hydrodeoolefinization method, which uses a multi-stage conventional hydrogenation reactor under hydrogenation conditions, and the liquid phase mixture is divided into stages and enters the reactor; the reaction is carried out in the catalyst bed layer area, and the reaction product after the reaction is partially recycled and mixed with fresh feed, and partially discharged from the reaction system to the subsequent separation device; the ratio of the circulating amount of the liquid hydroprocessing product to the feed is 1:1-5:1 by volume; and the hydrogenation process conditions are as follows: reaction temperature 80-180℃, pressure 1.5-2.0MPa, fresh feed volume space velocity 2.0-4.0h -1 .

[0006] Chinese patent application CN103805273A discloses a method for removing olefins from reforming generated oil. The reforming generated oil is first subjected to shallow hydrogenation under high space velocity, low hydrogen to oil ratio, low temperature and low pressure process conditions to control the bromine index in the generated oil, and then the hydrogenated generated oil is subjected to adsorption refining in a clay tower. The method of the invention cannot replace clay and still does not solve the problem of clay use.

[0007] In order to efficiently remove olefins from reforming generated oil, the following problems need to be solved: (1) hydrogen and reforming generated oil are mixed well and dissolved hydrogen is used; (2) hydrogen bubbles grow during the rising process in the liquid phase reactor, affecting the reaction; (3) the reaction conditions are well controlled to reduce the loss of aromatic hydrocarbons; (4) a suitable catalyst is selected to reduce investment costs; and (5) a suitable high-diameter ratio reactor and internal components are selected. SUMMARY

[0008] In view of the deficiencies of the prior art, a treatment method for efficiently removing olefins from reforming generated oil is developed. The method uses a liquid phase hydrogenation process, which greatly improves the olefin removal rate of reforming generated oil and significantly reduces the loss of aromatic hydrocarbons in reforming generated oil, on the one hand, and reduces the consumption of hydrogen, and on the other hand, ensures the stable and long-term operation of the olefin removal device.

[0009] The present application provides a method for completely replacing clay to remove olefins, which comprises sending reforming generated oil into a first hydrogenation reactor under liquid phase continuous hydrogenation treatment conditions, first contacting with a nickel-containing catalyst, and then the reaction product enters a second hydrogenation reactor and contacts with a noble metal-containing catalyst, wherein a high-efficiency gas-liquid mixer is arranged in front of the first hydrogenation reactor and / or the second hydrogenation reactor, and the reforming generated oil and hydrogen are passed through the high-efficiency gas-liquid mixer to make the hydrogen and the reforming generated oil intensively and quickly mix, and then saturated hydrogen-dissolved reforming generated oil is obtained and then enters the first hydrogenation reactor and / or the second hydrogenation reactor.

[0010] Through the olefin removal method of the present application, after the reforming generated oil is treated by the olefin removal method, the product obtained mainly contains benzene, toluene, xylene and other aromatic hydrocarbons, the bromine index is less than 20 mg Br / 100 g oil, the olefin removal rate is not less than 99 wt%, and the aromatic hydrocarbon loss is less than 0.1 wt%. In addition, using the olefin removal method of the present application, the consumption of hydrogen is significantly reduced, and the hydrogen consumption rate is not higher than 0.05 wt% relative to the weight of reforming generated oil.

[0011] A high-efficiency gas-liquid mixer is arranged before entering the hydrogenation reactor (the first hydrogenation reactor and / or the second hydrogenation reactor) to mix and dissolve hydrogen and the reforming product oil sufficiently to obtain the reforming product oil saturated with dissolved hydrogen. The high-efficiency gas-liquid mixer is a static mixer or a dynamic mixer. The static mixer can be selected from one or a combination of SV, SK, SX, SH and SL type static mixers. The dynamic mixer can be selected from one or a combination of a mixing pump, a vortex mixer, a supercritical mixer and a stirring mixer.

[0012] The present application adopts a combined catalyst to remove olefins in the reforming product oil, wherein the first hydrogenation reactor is filled with a hydrogenation refining catalyst with Ni as the active component and alumina as the carrier, and the content of Ni in the catalyst is not less than 3wt%, preferably 5wt%-30wt%. The second hydrogenation reactor is filled with a hydrogenation refining catalyst with noble metal as the active component and alumina as the carrier, and preferably one or more of Pt, Pd, Ru, Rh and other noble metals as the active component, and the content of the active component in the catalyst is not less than 0.1wt%, preferably 0.1wt%-0.5wt%.

[0013] According to the reaction characteristics of different hydrogenation deolefin catalysts, the reaction conditions of the first hydrogenation reactor are as follows: reaction temperature 40-120℃, pressure 1.0-3.0MPa, weight space velocity 0.5-20h -1 , hydrogen / oil volume ratio 2-200. The reaction conditions of the second hydrogenation reactor are as follows: reaction temperature 100-200℃, pressure 1.0-3.0MPa, weight space velocity 1-20h -1 , hydrogen / oil volume ratio 2-20.

[0014] The present application has the following technical effects:

[0015] According to the method of the present application, the reaction efficiency and production capacity can be effectively improved, the hydrogen consumption can be reduced, the process flow route is optimized, the stable and long-term operation of the deolefin device is ensured, and high-efficiency and low-consumption industrial production is realized. The method of the present application can completely replace the industrial white clay and molecular sieve refining non-hydrogen deolefin technology route, and the environmental protection problem of white clay waste and the like is solved to the maximum extent. BRIEF DESCRIPTION OF DRAWINGS

[0016] Figure 1 The figure is a reforming product oil hydrogenation deolefin process diagram of the present application.

[0017] Figure 2 The figure is a reforming product oil hydrogenation deolefin process diagram of another embodiment of the present application.

[0018] Wherein: 1 - reforming generated oil, 2 - hydrogen, 3, 4 - saturated hydrogen-dissolved reforming generated oil, 5 - hydrogen-refined reforming generated oil mixture, 6 - mixed gas containing undissolved hydrogen, 7 - hydrogen-refined reforming generated oil, A, A1, A2 - high-efficiency gas-liquid mixer, B - first hydrogenation reactor, C - first hydrogenation reactor, D - gas-liquid separator or stabilizer column. DETAILED DESCRIPTION

[0019] The application will be further described in details by examples. The features and advantages of the application will become more apparent through these descriptions. It should be understood that the specific embodiments described herein are only for illustration and explanation of the application, and do not limit the application.

[0020] The word "exemplary" used herein means "serving as an example, an implementation, or illustration". Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments. The embodiments are illustrated in the accompanying drawings, but are not necessarily drawn to scale unless otherwise indicated.

[0021] In addition, the technical features involved in the different embodiments of the application described below can be combined with each other as long as there is no conflict.

[0022] The application provides a treatment method for removing olefins in reforming generated oil, which comprises: under liquid-phase hydrogenation treatment conditions, passing the reforming generated oil and hydrogen through a high-efficiency gas-liquid mixer in sequence, and then respectively reacting with a nickel-containing and palladium-containing catalyst having catalytic hydrogenation effect in a first and a second hydrogenation reactor.

[0023] According to an embodiment of the application, the high-efficiency gas-liquid mixer can be provided with one or more.

[0024] According to an embodiment of the application, the reforming generated oil and hydrogen can be continuous feeding.

[0025] For the purpose of further illustrating the treatment process of the application, the process of the application is described herein. Take Figure 1 For example, the reforming generated oil 1 and hydrogen 2 enter the high-efficiency gas-liquid mixer A, and after being mixed intensively, form the uniform saturated hydrogen-dissolved reforming generated oil 3, which first enters the first hydrogenation reactor B to contact with the nickel-containing catalyst, and then enters the second hydrogenation reactor C to contact with the palladium-containing catalyst. The hydrogen-refined reforming generated oil mixture 5 after reaction enters the gas-liquid separator or stabilizer column D, to obtain the mixed gas 6 containing undissolved hydrogen and the hydrogen-refined reforming generated oil 7.

[0026] For example, the reforming generated oil 1 and hydrogen 2 enter the high-efficiency gas-liquid mixer A, and after being mixed intensively, form the uniform saturated hydrogen-dissolved reforming generated oil 3, which first enters the first hydrogenation reactor B to contact with the nickel-containing catalyst, and then enters the second hydrogenation reactor C to contact with the palladium-containing catalyst. The hydrogen-refined reforming generated oil mixture 5 after reaction enters the gas-liquid separator or stabilizer column D, to obtain the mixed gas 6 containing undissolved hydrogen and the hydrogen-refined reforming generated oil 7. Figure 2For example, the reformed oil 1 and a portion of hydrogen 2 enter the high-efficiency gas-liquid mixer A1, where they are vigorously mixed to form a uniformly saturated hydrogen-dissolved reformed oil 3, which first enters the first hydrogenation reactor B to contact the nickel-containing catalyst, and then is vigorously mixed with another portion of hydrogen 2 in the high-efficiency gas-liquid mixer A2 before entering the second hydrogenation reactor C to contact the palladium-containing catalyst. The hydrorefined reformed oil mixture 5 after the reaction enters the gas-liquid separator or stabilization tower D to obtain a mixed gas 6 containing undissolved hydrogen and a hydrorefined reformed oil 7.

[0027] According to one embodiment of the present invention, in order to ensure that the saturated dissolved hydrogen is in micro-nano bubbles during the rising process of the hydrogenation reactor, the height-to-diameter ratio of the first hydrogenation reactor and / or the second hydrogenation reactor is not less than 5.

[0028] According to one embodiment of the present invention, the reformed oil includes one or more of a reformed oil benzene fraction, a reformed oil BTX fraction, a full fraction reformed oil, and a reformed raffinate.

[0029] The present invention is further described below by way of examples, but the present invention is not limited thereto.

[0030] Example 1

[0031] (1) Preparation of nickel (Ni)-containing deolefination catalyst

[0032] Aluminum hydroxide dry rubber powder produced by the Changling Branch of Sinopec Catalyst Co., Ltd. using a sodium metaaluminate and aluminum sulfate precipitation method was mixed uniformly according to a mass ratio of powder: sesbania powder: nitric acid: acetic acid: citric acid: water = 50:1:2:3:3:40, and extruded into cylindrical strips with a diameter of 2 mm using an extruder. The wet strips were dried at 120°C for 12 hours and calcined at 600°C for 4 hours. The calcined support was impregnated in a nickel nitrate solution with a certain nickel content, so that the impregnation solution contained 10.0 wt% Ni (relative to the dry basis alumina mass). Using an equal volume impregnation method, the impregnated catalyst was dried at 120°C for 12 hours and then calcined at 450°C for 4 hours to obtain the finished nickel-containing catalyst Cat1-1.

[0033] (2) Preparation of palladium (Pd)-containing deolefination catalyst

[0034] The support was prepared in the same manner as in "(1) Preparation of nickel (Ni) deolefination catalyst". After the support was prepared, the impregnation solution contained 0.2 wt% Pd and 1.8 wt% Cl (relative to the mass of dry alumina) and a liquid / solid volume ratio of 1.5. The support and the impregnation solution were poured into a 500 mL flask and impregnated on a rotary vacuum evaporator (produced by Shanghai Yarong Biochemical Instrument Factory) at 30°C, 0.008 MPa, and a rotational speed of 0.03 m / s for 3 hours. The solid was vacuumed at 70°C to dry it and dried at 120°C for 12 hours. The catalyst was activated in dry air at 500°C and a gas / agent volume ratio of 700 for 4 hours, and then reduced with H2 at 480°C and a gas / agent volume ratio of 500 for 4 hours to obtain catalyst Cat2-1.

[0035] Example 2

[0036] use Figure 1 The reformate hydrodeolefination process shown. The first hydrogenation reactor B is loaded with Cat1-1 catalyst, and the second hydrogenation reactor C is loaded with Cat2-1 catalyst. The hydrogenation reactor has a height-to-diameter ratio of 8.

[0037] The reformed oil feedstock contains 83.78 wt% aromatics and has a bromine index of 3170 mg Br / 100 g oil. Reaction process conditions:

[0038] First hydrogenation reactor B: temperature 60 ° C, pressure 2.0 MPa, feed reaction, weight space velocity 3h -1 , the hydrogen-to-oil volume ratio is 20;

[0039] The second hydrogenation reactor C: temperature 130 ° C, pressure 2.0 MPa, feed reaction, weight space velocity 10h -1 , the hydrogen-to-oil volume ratio is 19.

[0040] After deolefination by hydrogenation, the reaction product contained 83.76 wt% of aromatic hydrocarbons, a bromine index of 18 mg Br / 100 g oil, an olefin removal rate of 99.43 wt%, and an aromatic hydrocarbon loss of 0.02 wt%.

[0041] Example 3

[0042] use Figure 2 The reformate hydrodeolefination process shown. The first hydrogenation reactor B is loaded with Cat1-1 catalyst, and the second hydrogenation reactor C is loaded with Cat2-1 catalyst. The hydrogenation reactor has a height-to-diameter ratio of 8.

[0043] The reformed oil feedstock contains 83.78 wt% aromatics and has a bromine index of 3170 mg Br / 100 g oil. Reaction process conditions:

[0044] First hydrogenation reactor B: temperature 60℃, pressure 2.0 MPa, feed reaction, weight space velocity 3h -1 , hydrogen / oil volume ratio 10;

[0045] Second hydrogenation reactor C: temperature 130℃, pressure 2.0 MPa, feed reaction, weight space velocity 10h -1 , hydrogen / oil volume ratio 9.

[0046] The amount of hydrogen entering the high-efficiency gas-liquid mixers A1 and A2 is the same.

[0047] After hydrogenation and de-olefination, the reaction product contains 83.77wt% aromatic hydrocarbons, the bromine index is 12mg Br / 100g oil, the olefin removal rate is 99.62wt%, and the aromatic hydrocarbon loss is 0.01wt%.

[0048] Comparative Example 1

[0049] Cat1-1 catalyst is used alone for de-olefination reaction, only the first hydrogenation reactor B is set, and the second hydrogenation reactor C is cancelled. The reforming generated oil raw material contains 83.78wt% aromatic hydrocarbons, and the bromine index is 3170mg Br / 100g oil. The reaction process conditions are:

[0050] First hydrogenation reactor B: temperature 100℃, pressure 2.0 MPa, feed reaction, weight space velocity 1h -1 , hydrogen / oil volume ratio 200.

[0051] After hydrogenation and de-olefination, the reaction product contains 56.96wt% aromatic hydrocarbons, the bromine index is 18mg Br / 100g oil, the olefin removal rate is 99.3wt%, and the aromatic hydrocarbon loss is 32.0wt%.

[0052] Comparative Example 2

[0053] Cat2-1 catalyst is used alone for de-olefination reaction, only the first hydrogenation reactor B is set, and the second hydrogenation reactor C is cancelled. The reforming generated oil raw material contains 83.78wt% aromatic hydrocarbons, and the bromine index is 3170mg Br / 100g oil. The reaction process conditions are:

[0054] First hydrogenation reactor B: temperature 150℃, pressure 2.0 MPa, feed reaction, weight space velocity 10h -1 , hydrogen / oil volume ratio 10.

[0055] After hydrogenation and de-olefination, the reaction product contains 83.56wt% aromatic hydrocarbons, the bromine index is 158mg Br / 100g oil, the olefin removal rate is 95.0wt%, and the aromatic hydrocarbon loss is 0.26wt%.

[0056] Example 4

[0057] (1) Preparation of a nickel (Ni) containing deolefin catalyst

[0058] The same as example 1, except that the impregnation solution contained 15.0 wt% Ni (relative to the mass of dry basis alumina), to produce the finished nickel containing catalyst Cat1-2.

[0059] (2) Preparation of a palladium (Pd) containing deolefin catalyst

[0060] The same as example 1, except that after the preparation of the support, the impregnation solution contained 0.15 wt% Pd, 0.10 wt% Pt, 1.8 wt% Cl (relative to the mass of dry basis alumina), to produce the catalyst Cat2-2.

[0061] Example 5

[0062] The deolefining process of the reforming generated oil was carried out as shown in Fig. 1. The first hydrogenation reactor B was packed with Cat1-2 catalyst, and the second hydrogenation reactor C was packed with Cat2-2 catalyst. The height to diameter ratio of the hydrogenation reactors was 10. Figure 1 The reforming generated oil feedstock contained 83.78 wt% aromatics, and the bromine index was 3170 mg Br / 100 g oil. The reaction process conditions were:

[0063] The first hydrogenation reactor B: the temperature was 80°C, the pressure was 2.0 MPa, the feedstock was reacted, the weight hourly space velocity was 10 h -1 , and the hydrogen to oil volume ratio was 20.

[0064] The second hydrogenation reactor C: the temperature was 120°C, the pressure was 2.0 MPa, the feedstock was reacted, the weight hourly space velocity was 10 h -1 , and the hydrogen to oil volume ratio was 19.

[0065] After the hydrogenation deolefining, the reaction product contained 83.77 wt% aromatics, the bromine index was 10 mg Br / 100 g oil, the olefin removal rate was 99.68 wt%, and there was no loss of aromatics.

[0066] Example 6

[0067] The deolefining process of the reforming generated oil was carried out as shown in Fig. 1. The first hydrogenation reactor B was packed with Cat1-2 catalyst, and the second hydrogenation reactor C was packed with Cat2-2 catalyst. The height to diameter ratio of the hydrogenation reactors was 8.

[0068] Figure 2 The reforming generated oil feedstock contained 83.78 wt% aromatics, and the bromine index was 3170 mg Br / 100 g oil. The reaction process conditions were:

[0069] The first hydrogenation reactor B: the temperature was 80°C, the pressure was 2.0 MPa, the feedstock was reacted, the weight hourly space velocity was 10 h -1 , and the hydrogen to oil volume ratio was 20.

[0070] The second hydrogenation reactor C: the temperature was 120°C, the pressure was 2.0 MPa, the feedstock was reacted, the weight hourly space velocity was 10 h -1 , and the hydrogen to oil volume ratio was 19.-1 hydrogen to oil volume ratio was 10;

[0071] Second hydrogenation reactor C: temperature 120℃, feed reaction under pressure 2.0 MPa, weight space velocity was 10 h -1 hydrogen to oil volume ratio was 9.

[0072] The amount of hydrogen entering the high-efficiency gas-liquid mixers A1 and A2 was the same.

[0073] The reaction product contained 83.77wt% of aromatic hydrocarbons, the bromine index was 8 mg Br / 100g oil, the olefin removal rate was 99.75wt%, and there was no loss of aromatic hydrocarbons.

[0074] Comparative Example 3

[0075] The Cat1-2 catalyst was used alone for olefin removal reaction, only the first hydrogenation reactor B was set, and the second hydrogenation reactor C was cancelled. The reforming generated oil raw material contained 83.78wt% of aromatic hydrocarbons, and the bromine index was 3170 mg Br / 100g oil. The reaction process conditions were:

[0076] First hydrogenation reactor B: temperature 100℃, feed reaction under pressure 2.0 MPa, weight space velocity was 6 h -1 hydrogen to oil volume ratio was 200.

[0077] After hydrogenation and olefin removal, the reaction product contained 67.0wt% of aromatic hydrocarbons, the bromine index was 14 mg Br / 100g oil, the olefin removal rate was 99.56wt%, and the loss of aromatic hydrocarbons was 20.0wt%.

[0078] Comparative Example 4

[0079] The Cat2-2 catalyst was used alone for olefin removal reaction, only the first hydrogenation reactor B was set, and the second hydrogenation reactor C was cancelled. The reforming generated oil raw material contained 83.78wt% of aromatic hydrocarbons, and the bromine index was 3170 mg Br / 100g oil. The reaction process conditions were:

[0080] First hydrogenation reactor B: temperature 150℃, feed reaction under pressure 2.0 MPa, weight space velocity was 10 h -1 hydrogen to oil volume ratio was 10.

[0081] After hydrogenation and olefin removal, the reaction product contained 83.63wt% of aromatic hydrocarbons, the bromine index was 120 mg Br / 100g oil, the olefin removal rate was 96.2wt%, and the loss of aromatic hydrocarbons was 0.18wt%.

[0082] From the above examples and comparative examples, it can be seen that the olefin removal method of the present application has an olefin removal rate of the reforming generated oil of more than 99% under mild reaction conditions, and an aromatic loss of less than 0.1%, and the bromine index of the reforming generated oil after the olefin removal treatment is less than 20 mg Br / 100 g oil.

[0083] In the description of the present application, it should be noted that the terms "upper", "lower", "inner", "outer", "front", "back", "left", "right" and the like indicate the orientation or positional relationship based on the working state of the present application, and are only for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as a limitation on the present application.

[0084] The above describes the present application in combination with the preferred embodiments, but these embodiments are only exemplary and serve only to illustrate. On this basis, various substitutions and improvements can be made to the present application, which all fall within the scope of protection of the present application.

Claims

1. A green deolefination method that completely replaces clay, characterized in that: The method comprises: under liquid-phase continuous hydrogenation treatment conditions, feeding reformed oil into a first hydrogenation reactor, first contacting it with a nickel-containing catalyst, and then feeding the reaction product into a second hydrogenation reactor, contacting it with a noble metal-containing catalyst, wherein a high-efficiency gas-liquid mixer is provided before the first hydrogenation reactor and / or the second hydrogenation reactor, and the reformed oil and hydrogen are passed through the high-efficiency gas-liquid mixer to achieve enhanced and rapid mixing of the hydrogen and the reformed oil to obtain hydrogen-saturated reformed oil, which then enters the first hydrogenation reactor and / or the second hydrogenation reactor; The reaction conditions of the first hydrogenation reactor are: reaction temperature 40 ~ 120 ° C, pressure 1.0 ~ 3.0 MPa, weight space velocity 0.5 ~ 20 h -1 , hydrogen-oil volume ratio 2 ~ 200; The bromine index of the product obtained after deolefination of the reformed oil is less than 20 mg Br / 100 g oil, the olefin removal rate is not less than 99 wt%, and the aromatics loss is less than 0.1 wt%.

2. The deolefination method according to claim 1, wherein One or more high-efficiency gas-liquid mixers are provided.

3. The deolefination method according to claim 1 or 2, wherein: The high-efficiency gas-liquid mixer is a static mixer or a dynamic mixer.

4. The deolefination method according to claim 1, wherein The first hydrogenation reactor is loaded with a hydrorefining catalyst with Ni as an active component and alumina as a carrier, and the content of Ni in the catalyst is not less than 3 wt% by weight.

5. The deolefination method according to claim 4, wherein The first hydrogenation reactor is loaded with a hydrorefining catalyst, and the content of Ni in the catalyst is 5 wt% to 30 wt%.

6. The deolefination method according to claim 1, wherein The second hydrogenation reactor is filled with a hydrorefining catalyst with a precious metal as an active component and alumina as a carrier, and the content of the active component in the catalyst is not less than 0.1 wt% by weight.

7. The deolefination method according to claim 6, wherein: The hydrorefining catalyst loaded in the second hydrogenation reactor has one or more precious metals selected from Pt, Pd, Ru and Rh as active components.

8. The deolefination method according to claim 6, wherein The second hydrogenation reactor is filled with a hydrorefining catalyst, and the content of active components in the catalyst is 0.1 wt% to 0.5 wt% by weight.

9. The deolefination method according to claim 1, wherein The height-to-diameter ratio of the first hydrogenation reactor and / or the second hydrogenation reactor is not less than 5.

10. The deolefination method according to claim 1, wherein The reaction conditions of the second hydrogenation reactor are: reaction temperature 100 ~ 200 ° C, pressure 1.0 ~ 3.0 MPa, weight space velocity 1 ~ 20 h -1 , hydrogen-oil volume ratio is 2~20.

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